Methods for storing hydrogen in a salt cavern

ABSTRACT

A novel method for storing high purity hydrogen into a salt cavern is provided. Particularly, the storage process involves confining the high purity hydrogen at a certain pressure in a salt cavern without seepage or leakage of the stored hydrogen through the salt cavern walls. The pressure in the cavern is maintained during storage of the high purity hydrogen.

RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.14/182,582, which is a continuation-in-part of U.S. Pat. No. 8,690,476,filed on May 25, 2012, each of which is hereby incorporated by referencein its entirety.

FIELD OF THE INVENTION

The present invention relates to a novel method for storing high purityhydrogen into a salt cavern. Particularly, the storage process involvesstoring high purity hydrogen into a salt cavern without seepage of thestored hydrogen across or through the walls of the salt cavern.

BACKGROUND OF THE INVENTION

Hydrogen is supplied to customers connected to a hydrogen pipelinesystem. Typically, the hydrogen is manufactured by steam methanereforming in which a hydrocarbon and steam are reacted at hightemperature in order to produce a synthesis gas containing hydrogen andcarbon monoxide. Hydrogen is separated from the synthesis gas to producea hydrogen product stream that is introduced into the pipeline systemfor distribution to customers that are connected to the pipeline system.Alternatively, hydrogen produced from the partial oxidation of ahydrocarbon can be recovered from a hydrogen rich stream. Typically,hydrogen is supplied to customers under agreements that requireavailability and on stream times for the steam methane reformer orhydrogen recovery plant. When a steam methane reformer is taken off-linefor unplanned or extended maintenance, the result could be a violationof such agreements. Additionally, there are instances in which customerdemand can exceed hydrogen production capacity of existing plants.Having a storage facility to supply back-up hydrogen to the pipelinesupply is therefore desirable in connection with hydrogen pipelineoperations. Considering that hydrogen production plants on average haveproduction capacities that are roughly 50 million standard cubic feetper day or greater, a storage facility for hydrogen that would allow aplant to be taken off-line, to be effective, would need to have storagecapacity in the order of 1 billion standard cubic feet or greater.

The large storage capacity can be met by means of salt caverns to storethe hydrogen underground. Low purity grades of hydrogen (i.e., below 95%purity) as well as other gases have been stored in salt caverns. Saltcaverns are large underground voids that are formed by adding freshwater to the underground salt, thus creating brine, which is oftenreferred to as solution mining. Caverns are common in the gulf states ofthe United States where demand for hydrogen is particularly high. Suchhydrogen storage has taken place where there are no purity requirementsor less stringent (<96% pure) requirements placed upon the hydrogenproduct. In such case, the stored hydrogen from the salt cavern issimply removed from the salt cavern without further processing.

High purity (e.g., 99.99%) hydrogen storage within salt caverns presentsseveral challenges. For example, storing large quantities (e.g., greaterthan 100 million standard cubic feet) of pure (e.g., 99.99%) gaseoushydrogen in underground salt caverns consisting of a minimum salt purityof 75% halite (NaCl) or greater without measurable losses of the storedhydrogen is difficult based on the properties of hydrogen. Hydrogen isthe smallest and lightest element within the periodic table of elements,having an atomic radius measuring 25 pm+/−5 pm. Further, hydrogen isflammable, and therefore a very dangerous chemical if not handledproperly. Salt caverns consist of salt walls that have various ranges ofpermeability (e.g., 0-23×10^-6 Darcy) that if not controlled properlycould easily allow gaseous hydrogen to permeate through the salt wallsand escape to the surface of the formation. If the stored hydrogenwithin an underground salt formation was to escape and permeate throughthe salt formation to the surface, a dangerous situation could arisewith fatality potential or immense structural damage potential.Consequently, high purity hydrogen is typically considered one of themost difficult elements to contain within underground salt formations.

As will be discussed, among other advantages of the present invention,an improved method and system for storing hydrogen in a salt cavern isdisclosed.

SUMMARY OF THE INVENTION

The invention relates, in part, to a method and system for storing highpurity hydrogen into a salt cavern. The cavern pressure has been foundto affect the ability to form a leak-tight cavern not susceptible tohydrogen leakage. It has been found that maintaining the cavern pressurewithin a specific pressure range improves the structural integrity ofthe salt cavern. The method and system for storage as will be explainedbelow is capable of storing high purity hydrogen without detection ofsubstantial seepage through the salt cavern. The storage process isconducive for the storage of hydrogen having purity levels from at least95% up to about 99.999% or greater.

In a first aspect, a method for storing hydrogen product in a saltcavern is provided. Hydrogen product is removed from a hydrogenpipeline. The hydrogen product is compressed to produce a compressedhydrogen product. The compressed hydrogen product is introduced into thesalt cavern to produce stored hydrogen within the salt cavern. Asubstantially impermeable permeation barrier is created to the storedhydrogen along at least a portion of the walls of the salt cavern bystoring the stored hydrogen at a pressure that is between apredetermined lower limit and a predetermined upper limit.

In a second aspect, a method for improved confinement of stored hydrogenwithin a substantially impermeable permeation barrier of a salt cavernis provided. Hydrogen product is removed from a hydrogen pipeline. Thehydrogen product is compressed to produce a compressed hydrogen product.The cooling rate of an after cooler situated downstream of a compressoris regulated to manipulate a heat of compression within the compressedhydrogen product. The compressed hydrogen product is introduced througha well casing extending into the salt cavern. At least a portion of theheat of compression is transferred from the compressed hydrogen productto the well casing. The temperature of the well casing is increased bythe transfer of heat from the compressed hydrogen product to increasethe ductility of the casing and suppress the onset of hydrogenembrittlement along the casing, thereby maintaining a seal between thecasing and the cavern to improve confinement of the stored hydrogen. Thecompressed hydrogen product from the casing is introduced into the saltcavern to produce stored hydrogen within the salt cavern at a pressurebetween a predetermined lower limit and predetermined upper limit. Asubstantially impermeable permeation barrier to the stored hydrogen iscreated along at least a portion of the walls of the salt cavern bystoring the stored hydrogen at a pressure that is between apredetermined lower limit and a predetermined upper limit.

In a third aspect, a method for maintaining a substantially impermeablepermeation barrier in a salt cavern contained a stored gas is provided.A substantial portion of the stored gas from the salt cavern iswithdrawn to a level at which a pressure of the remaining portion of thestored hydrogen is reduced below a predetermined lower limit. Asufficient amount of compressed fluid is introduced into the salt cavernto reduce an effective volume of the salt cavern and pressurize theremaining portion of the stored gas to increase the pressure above thepredetermined lower limit. A substantially impermeable permeationbarrier to the stored gas at the pressure above the predetermined lowerlimit is created along at least a portion of the walls of the saltcavern.

In a fourth aspect, a method for storing hydrogen product in a saltcavern is provided. Hydrogen product is removed from a hydrogen source.The hydrogen product is introduced into the salt cavern to producestored hydrogen within the salt cavern. The seepage of the storedhydrogen is reduced through walls of the salt cavern by maintaining thestored hydrogen at a pressure between a predetermined lower limit and apredetermined upper limit, thereby creating a substantially impermeablepermeation barrier to the stored hydrogen along at least a portion ofthe walls of the salt cavern.

In a fifth aspect, an underground hydrogen storage cavern is provided.The cavern is formed by solution mining an underground salt formation toform a cavity defined by the salt walls and filling the cavity with acompressed hydrogen gas. The salt cavern has been modified to include asubstantially impermeable permeation barrier to stored hydrogen withinthe storage cavern along at least a portion of the walls.

BRIEF DESCRIPTION OF THE DRAWINGS

The objectives and advantages of the invention will be better understoodfrom the following detailed description of the preferred embodimentsthereof in connection with the accompanying figures wherein like numbersdenote same features throughout and wherein:

FIG. 1 shows a fragmentary schematic of a protocol for introducing andstoring hydrogen to a hydrogen pipeline incorporating the principles ofthe invention;

FIG. 2 shows a salt cavern having a substantially impermeable permeationbarrier; and

FIG. 3 shows a brine pond reservoir for providing brine into the saltcavern of FIG. 2 as needed to increase the cavern pressure to apredetermined pressure threshold for maintaining the substantiallyimpermeable permeation barrier; and

FIG. 4a shows a salt cavern wall containing stored hydrogen at apressure below a lower limit in which hydrogen seepage across the saltcavern occurs;

FIG. 4b shows a salt cavern wall containing stored hydrogen at apressure within the pressure threshold limits so as to form asubstantially impermeable permeation barrier in accordance with theprinciples of the present invention;

FIG. 4c shows a salt cavern wall containing stored hydrogen at apressure above the upper limit in which hydrogen leakage occurs;

FIG. 5a shows a geothermal temperature profile generated during amechanical integrity test; and

FIG. 5b shows a leakage detection system that can be employed during themechanical integrity verification of the salt cavern.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, all concentrations are expressed as volumetricpercentages. With reference to FIG. 1, a hydrogen storage and processingfacility 1 is illustrated that is designed to remove hydrogen productfrom a hydrogen pipeline 2 during periods of low customer demand andstore such hydrogen product within a salt cavern 3 as stored hydrogen 4.During periods at which demand for the hydrogen product exceeds thecapabilities of the hydrogen pipeline 2 to supply hydrogen product tocustomers, stored hydrogen 4 can be removed from the salt cavern 3 andreintroduced into the hydrogen pipeline 2. In a manner that will bediscussed, a substantially impermeable permeation barrier within thesalt cavern 3 can be formed and continuously maintained for storinghydrogen product. The ability to store hydrogen product within such asalt cavern 3 having a substantially impermeable permeation barrier canadvantageously produce a substantially leak-tight salt cavern not proneto seepage of stored hydrogen product through the salt cavern walls, astypically occurs with conventional salt caverns. The term “permeationbarrier” as used herein is intended to refer to the walls of the saltcavern that when pressurized and/or thermally activated, restricts thepassage of hydrogen flow. As a result, there is a reduction in the sizeand/or the quantity of interconnected pores or voids within the walls ofthe salt cavern that allow the permeation of hydrogen gas molecules intothe wall or contaminant gas molecules through the wall. Accordingly,this reduction in the size and/or quantity of interconnected pores orvoids substantially minimizes or prevents the availability of flow pathsfor high purity hydrogen molecules, preferably of at least 95% purityand above, from escaping therein and thereafter through the surroundingrock salt of the salt cavern.

As known in the art, salt cavern 3 is formed by solution mining in whichwater is injected through a pipe known as a brine string 10. The waterdissolves the salt, and the resulting brine during the mining operationis returned through the annular space (not shown) formed in the finalwell casing 12 or other conduit between the inner wall of the final wellcasing 12 and the outer wall of the brine string 10. After the solutionmining operation is complete, the residual brine in the salt cavern 3can be removed through the brine string 10 by pressure displacementresulting from injection of hydrogen through the final casing 12 orother conduit. Once the brine level reaches the bottom of the brinestring 10, a top section of the brine string 10 is sealed off by valve216 and a residual brine layer 20, also known as a brine sump, mayremain in the salt cavern 3 at the bottom portion 207.

The rock salt walls of the salt cavern deposit into thick layers overtime. The deposited layers are gradually covered and buried byoverburden sediments. The weight or pressure of such overburdensediments causes the salt formations to form densified structures, whichtend to undergo viscoplastic slippage or deformation to create densifiedmircrocracks. Such slippage causes the grains of the salt to possess aninherent porosity, which is generally somewhat pervious to hydrogen.While the salt generally has low permeability and porosity rendering itimpermeable to hydrocarbons, the salt is significantly more prone tohydrogen permeation by virtue of hydrogen's small atomic radius.

When customer demand for the hydrogen, supplied by hydrogen pipeline 2is low or for any reason, production exceeds demand, a hydrogen stream13 can be removed from the hydrogen pipeline 2 or alternatively receivedfrom another hydrogen production or storage source (not shown) andintroduced into the salt cavern 3. “Hydrogen pipeline” or “hydrogenproduct pipeline” as used herein is intended to refer any conduit orpassageway extending between the salt cavern 3 and the hydrogenproduction or storage source. In this regard, referring to FIG. 1, valve24 is open to allow a portion of the product hydrogen in pipeline 2 toenter leg “A” of flow network 5. As used herein and in the claims, theterm “legs” means flow paths within the flow network 5 that are formedby suitable conduits. Such conduits would be positioned to conduct theflow of the hydrogen streams within the flow network 5 as illustrated.Bypass valve 14 is set in a closed position, and valve 15 is set in anopen position and valve 20 and valve 303 are set in a closed position toallow hydrogen stream 13 to be compressed in a hydrogen compressor 7 toproduce a compressed hydrogen stream 16. Hydrogen compressor 7 can beany known compressor as used in the art, and is typically a compressorhaving a reciprocating piston. Hydrogen compressor 7 incorporates afirst stage 8 and a second stage 9 in series with interstage coolingbetween stages and an aftercooler 10 which can be employed to remove theheat of compression. Alternatively, and as will be explained in greaterdetail below, the heat of compression can be transferred to thecompressed hydrogen stream 16 when entering the salt cavern 3, as partof a thermal activation of the salt cavern 3. The compressor 7 isconventionally controlled to maintain the inlet pressure at a targetsuction pressure to maintain energy efficient operation of thecompressor 7.

The compressed hydrogen stream 16 is introduced into the salt cavern 3to form the stored hydrogen 4. The compressed hydrogen stream 16continues to flow through the first leg “A”. The compressed hydrogenstream 16 thereafter enters well-casing or conduit 12 (FIG. 2), which isconnected to a transfer well head assembly 202, and thereafter into anannular flow area (not shown) within final well casing 12 (between theinside of final well casing 12 and brine string 10) from which thecompressed hydrogen feed stream 16 enters salt cavern 3. Flow orificemeter 17, pressure transmitter 18 and temperature transmitter 19 can beused to determine the quantity of compressed hydrogen stream 16 that isintroduced into the salt cavern 3.

FIG. 2 shows the cavern 3 of FIG. 1 in isolation. The pressure of thestored hydrogen 4 exerts a pressure, denoted as “P”, against the walls203 of the salt cavern 3. The cavern depth that starts at the top of thesalt and ends at the bottom of the salt cavity is denoted as “d” and isdefined as the vertical distance spanning from the top-most portion 204to the bottom-most portion 207 of the salt cavern 3. The pressureexerted by the stored hydrogen 4 against the salt cavern walls 203 ismaintained above a lower threshold limit and below an upper thresholdlimit such that there is a reduction in the size and the quantity ofinterconnected pores or voids within the walls 203 of the salt to form asubstantially impermeable permeation barrier 206. FIG. 2 shows that thesubstantially impermeable permeation barrier 206 extends along theentire edge or boundary of the cavern 3. The substantially impermeablepermeation barrier 206 formed along the salt cavern walls has a reducedamount of interconnected porosity such that there are few or virtuallyno pathways for hydrogen to diffuse therethrough. The substantiallyimpermeable permeation barrier 206 as defined herein substantiallyprevents all of the molecules of the stored hydrogen 4 from passingtherethrough and seeping into the rock salt 205, as shown in FIG. 2. Itshould be understood that the substantially impermeable permeationbarrier 206 in FIGS. 1 and 2 is shown as having a finite thickness onlyfor purposes of illustrating the principles of the present invention. Inaddition, not maintaining the pressure between a lower threshold limitand an upper threshold limit for short periods of time in commercialoperation is not believed to have deleterious effects on the maintenanceof the barrier, and as such is contemplated by the present invention.

The lower limit has been found by the inventors to be greater than about0.2 psi per liner foot of cavern depth. In this example, at a caverndepth of about 2500 feet as shown in FIG. 2, the minimum pressure mustbe maintained at greater than about 500 psig to allow formation of thesubstantially impermeable permeation barrier 206. In a preferredembodiment, the minimum pressure may be regulated so as to counteractthe tendency of the salt cavern 3 to undergo creep closure, which occurswhen the overburden cavern pressures are greater than the pressurewithin the cavern which causes the salt cavern 3 to close in and reducethe overall physical storage volume. Unlike the prior art, the presentinvention eliminates permeability of the salt cavern but still allowsfor counterbalancing of the creep closure.

Although maintaining the cavern 3 at a pressure exceeding the lowerlimit is advantageous, the inventors have also discovered an upper limitfor pressure which cannot be exceeded. The upper limit has been found tobe less than about 1 psi per liner foot of cavern depth. In thisexample, at a cavern depth of about 2500 feet as shown in FIG. 2, themaximum pressure must be maintained at a pressure lower than 2500 psigto allow for proper maintenance of the substantially impermeablepermeation barrier 206. Exceeding the upper limit can cause the saltwalls 203 to fracture, thereby causing the stored hydrogen 4 to flowupward through the fractures into the rock salt 205 and eventually tothe surface, which could cause a potential safety hazard if the properconditions existed such that the released hydrogen ignited.

Exploded views of a portion of the substantially impermeable permeationbarrier 206 in FIG. 2 that is circumscribed by the rectangular dottedregion is illustrated in FIGS. 4A-4C under three different cavernpressure scenarios. FIG. 4A shows that when the stored hydrogen 4 ismaintained in the cavern 3 at a pressure substantially less than 0.2 psiper foot of cavern depth, hydrogen seepage occurs across the salt walls203. FIG. 4A indicates that the porosity or voids along at least certainportions of the salt walls 203 are marginally large enough to allowavailability of hydrogen molecules to flow therethrough. Such a scenariois representative of the stored hydrogen 4 being stored below the lowerlimit.

FIG. 4C, on the other hand, is indicative of one or more cracks orfractures along the salt walls 203 which can potentially form when thestored hydrogen 4 is maintained in the cavern 3 at a pressuresubstantially greater than about 1 psi per foot of cavern depth. Thecracks are sufficiently large to allow hydrogen to leak therethrough. Byway of comparison, the hydrogen leakage across the salt walls 203 occursat a higher flow rate than the hydrogen seepage in FIG. 4A by virtue ofthe cracks creating larger flow paths. The scenario of FIG. 4C isrepresentative of the stored hydrogen 4 being stored above the upperlimit.

FIG. 4B shows successful formation of the substantially impermeablepermeation barrier 206 in which molecules of the stored hydrogen 4remain entirely confined within the interior volume of the salt cavern3. FIG. 4B shows that the stored hydrogen 4 is maintained in the cavern3 at a pressure greater than 0.2 psi per foot of cavern depth but lessthan 1 psi per foot of cavern depth. The substantially impermeablepermeation barrier 206 creates a reduction in the size and quantity ofinterconnected pores or voids within the salt walls 203, therebyreducing or preventing the availability of flow paths for high purityhydrogen molecules from escaping the interior volume of the salt cavern3.

In a preferred embodiment, the stored hydrogen 4 can be maintained in apressure range that can vary between 0.4 to 0.8 psi per liner foot ofcavern depth to form and maintain a substantially impermeable permeationbarrier 206 that can confine the stored hydrogen 4 within the walls 203of the salt cavern 3. The substantially impermeable permeation barrier206 is formed by reducing the porosity of the cavern walls sufficientlyenough to prevent the passage of high purity hydrogen molecules. In apreferred embodiment, the salt cavern 3 can be stored with 99.99% purehydrogen gas without detectable seepage through the barrier 206.

Effectiveness of the substantially impermeable permeation barrier 206can be assessed with pressure and temperature measurements. Forinstance, a pressure measurement is made in the cavern 3 by a downholepressure transducer 208 to ensure the proper pressure range ismaintained. Alternatively, a local cavern wellhead surface pressuremeasurement device (not shown), which may be located within the cavernwellhead assembly 202, can be employed for measuring pressure. Thepressure transducer 208 extends through the well-casing or conduit 12 ofthe cavern well head assembly 202.

Alternatively or in addition to pressure gauges, one or more temperaturegauges are placed at various locations within the interior volume of thesalt cavern 3 to monitor the integrity of the substantially impermeablepermeation barrier 206. For example, a downhole temperature gauge canextend through the conduit 12 and be positioned at a predeterminedlocation within the stored hydrogen 4. Because hydrogen displays anegative Joule-Thompson coefficient, any seepage of the stored hydrogen4 through walls 203 will manifest itself as a localized temperatureexcursion. Estimated temperature excursions as a result of seepage ofhydrogen leakage have been observed to be on the order of 4° F. forpressure loss of and about 1200 psi in the cavern 3.

Generally speaking, if it is determined that leakage is occurringthrough the cavern 3, the pressure of the stored hydrogen 4 can beadjusted as needed to form a substantially impermeable permeationbarrier 206 that is less prone to leakage of the stored hydrogen 4therethrough. For example, if the downhole pressure transducer 208 showsthat the pressure in the cavern 3 has exceeded the upper limit, aportion of the stored hydrogen 4 can be withdrawn from cavern 3 untilthe pressure falls to below the upper limit. Alternatively, if thedownhole pressure transducer 208 indicates that the pressure in thecavern 3 has fallen below the lower limit, a portion of the hydrogenproduct from the pipeline 2 can be introduced into the cavern 3 untilthe pressure of the cavern 3 increases to at least slightly above thelower limit. As a result, a critical mass of stored hydrogen 4 is alwayskept in cavern 3 to maintain the substantially impermeable permeationbarrier 206.

Large swings in customer demand for hydrogen product from the hydrogenpipeline 2 can significantly alter the amount of stored hydrogen 4required to be withdrawn from the cavern 3 and directed to the hydrogenpipeline 2. This in turn increases the variation in pressure in thecavern 3. The pressure in the cavern 3 may vary to the extent that thepressure falls outside the predetermined upper and lower limits forshort periods of time. As a result, real-time adjustments are performedto ensure that the substantially impermeable permeation barrier 206 tothe stored hydrogen 4 is restored during operation of the cavern 3.

For instance, when customer demand is below production capabilities, or,for any reason, demand may fall below production, the cavern pressuremay exceed the upper limit as a result of an increased amount ofhydrogen product from the pipeline 2 being introduced into the cavern 3.The present invention may utilize one or more downhole temperature andpressure gauges 501 and 208 (FIGS. 2 and 5) to detect that the pressureof the stored hydrogen 4 has exceeded an upper limit for short periodsof time. After measuring and detecting the elevated pressure, at least aportion of the stored hydrogen 4 from the cavern 3 can be withdrawn andreturned to the hydrogen product pipeline 2. Referring to FIG. 1, valve20 would be opened to allow a portion of the stored hydrogen 4 to bedischarged from the cavern 3 as a crude hydrogen stream 21. Because thepressure of the stored hydrogen 4 is higher than that of the pipeline 2in this particular example, the crude hydrogen stream 21 readily flowsthrough the second leg “B” of flow network 5. A sufficient amount ofstored hydrogen 4 can be withdrawn so that the pressure of the storedhydrogen 4 remaining in the cavern 3 falls below the upper limit. As thepressure decreases below the upper limit, the pressure in the cavern isinsufficient to have a tendency to fracture the walls 203 of the saltcavern 3, and a substantially impermeable permeation barrier 206 isre-established along the walls 203 of the cavern 3. When the appropriateamount of stored hydrogen 4 has been removed, valve 20 is closed toisolate the cavern 3. Cavern pressure and temperature can be monitoredto ensure that the substantially impermeable permeation barrier 206remains within the predetermined lower and upper limits.

In another scenario, customer demand may fall below productioncapabilities, or, for any reason, demand may fall below production, suchthat a real-time analysis of the cavern pressure indicates that thepressure is trending upwards and approaching the upper limit. Afterdetecting the upward trend and in response thereto, at least a portionof the stored hydrogen 4 can be withdrawn to the hydrogen productpipeline 2. Withdrawal of stored hydrogen 4 continues until the pressureof the stored hydrogen 4 is considered to fall below the upper limit. Inone example, withdrawal of the stored hydrogen 4 continues until thepressure is determined to be sufficiently below the upper limit, suchthat the inherent pressure fluctuation of the stored hydrogen 4 in thecavern 3 does not exceed the upper limit. This downward adjustment inpressure allows the substantially impermeable permeation barrier 206 tothe stored hydrogen 4 to be maintained.

During the operation of the salt cavern 3, there may be instances whencustomer demand may be greater than the supply of the hydrogen in theproduct pipeline 2, or, for any reason, demand exceeds production ofhydrogen. As a result, the pressure of the stored hydrogen 4 may fallbelow the lower limit for short periods of time. In response to suchmeasurement and detection, a portion of hydrogen product from thehydrogen product pipeline 2 can be introduced from the hydrogen pipeline2 into the salt cavern 3 to increase the pressure of the stored hydrogen3 above the lower limit. Referring to FIG. 1, valve 24 is set in theopen position and bypass valve 14 is set in the open position, as thepressure in the pipeline 2 in this particular example is sufficient forthe hydrogen product to free flow along leg “A” without requiringpressurization by compressor 7. Valve 15 is opened and valve 20 isclosed. The hydrogen product introduced into the cavern 3 increases thepressure in the cavern 3 that is exerted against the walls 203 of thecavern 3. The porosity of the walls 203 of salt cavern 3 is partiallycompressed, which in turn reduces the voids and/or grain boundaries ofthe salt walls 203 to a size substantially small enough to prevent thestored hydrogen 4 from passing therethrough. Cavern pressure andtemperature can be monitored to ensure that the substantiallyimpermeable permeation barrier 206 is adequate. When the appropriateamount of hydrogen product from the pipeline 2 has been introduced intothe cavern 3, valve 15 is closed to isolate the cavern 3. As thepressure in the cavern 3 increases above the lower limit, the pressureis sufficient to have a tendency to counteract creep closure of thewalls 203 of the salt cavern 3, and a substantially impermeablepermeation barrier 206 to the stored hydrogen 4 is re-established alongthe walls 203 of the cavern 3.

Still further, customer demand can be greater than the supply of thehydrogen in the product pipeline 2, or, for any reason, demand exceedsproduction of hydrogen such that a real-time analysis of the pressureindicates that the pressure is trending downwards and approaching thelower limit. After detecting the downward trend and in response thereto,a portion of the hydrogen product from the hydrogen pipeline 2 can beintroduced into the salt cavern 3 until the pressure of the storedhydrogen 4 within the cavern 3 is determined to increase above the lowerlimit. In one example, hydrogen product from the hydrogen pipeline 2continues to be introduced into the cavern 3 until the pressure in thecavern 3 increases sufficiently above the lower limit, such thatinherent pressure fluctuation in the stored hydrogen 4 does not fallbelow the lower limit. This upward adjustment in pressure thereforeallows the substantially impermeable permeation barrier 206 to thestored hydrogen 4 to be maintained.

In an alternative embodiment, there will be instances when a hydrogengeneration facility is taken off-line or when demand for hydrogen bycustomers otherwise exceeds the available production capabilities,either of which necessitates removal of substantially all of the storedhydrogen 4 from the salt cavern 3. In such a case, the cavern 3 canapproach a hydrogen depleted state for a sustained period of time duringoperation of the cavern 3. A cavern in a “hydrogen depleted state” asdefined herein refers to a cavern containing an insufficient quantity ofhydrogen such that the cavern pressure is below the lower limit asdefined herein for a sustained period of time. In one example, thehydrogen depleted state may be about 50-90% below the lower limit. Inorder to maintain the substantially impermeable permeation barrier 206,fluid can be temporarily introduced into the salt cavern 3 to maintainthe pressure in the cavern 3 necessary for the substantially impermeablepermeation barrier 206. The term “fluid” as used herein is intended tocover either a gas phase, liquid phase or a combination thereof. FIG. 3describes one possible embodiment of a brine pond system 300 forachieving continued maintenance of the substantially impermeablepermeation barrier 206. Brine 315 from a brine pond reservoir 301 can beintroduced into the salt cavern 3 so as to occupy the depleted cavern 3.The brine pond system 300 includes a reservoir 301 and sump pump 302 fortransporting brine 302 into the salt cavern 3 as needed to increase thecavern pressure beyond the lower limit for maintaining the substantiallyimpermeable permeation barrier 206. The brine pond 300 also includes aflow network 318 consisting of a discharge leg “C”, a return leg “D”,valve 303 and valve 304. The flow network 318 allows the brine 315 to betransported to the salt cavern 3 through leg “C” and returned thereafterback into the brine pond 301 through leg “D”.

In operation, brine 315 exits from the bottom of the brine pondreservoir 301 utilizing sump pump 302, which pressurizes and transportsthe brine 315 along flow leg “C” as brine stream 316. Valve 303 isclosed, and valve 304 is set in the open position to allow the brinestream 316 to flow through a conduit 319 connected to the transfer wellhead valve 202 and thereafter into an annular flow area (not shown)within final well casing 12 (between the inside of final well casing 12and brine string 10) from which the brine stream 316 enters salt cavern3.

The brine 315 occupies the bottom portion 207 of the cavern 3. As aresult, the usable volume of the cavern 3 is reduced. The reduction involume of the salt cavern 3 allows for the remaining stored hydrogen 4contained in the interior volume of the cavern 3 to occupy a smallerstorage volume, thereby increasing the pressure of the cavern 3. Brine315 continues to enter salt cavern 3 through brine string 10 untildownhole pressure transducer 208 detects that the cavern pressure hasreached above the lower limit. Alternatively, wellhead pressuremeasuring devices (not shown), which may be located within the cavernwellhead assembly 202, can be utilized to detect cavern pressure. Whenthe desired caver pressure is detected, valve 304 can be closed toisolate the cavern 3. In the manner described herein, the substantiallyimpermeable permeation barrier 206 can be maintained, even though thecavern 3 has been depleted of hydrogen.

Other variations are possible and are within the scope of the presentinvention. For instance, the brine 315 may be introduced into the cavern3 so as to displace the stored hydrogen 4 therein. As pressurized brine315 enters brine string 315, the stored hydrogen 4 can be displacedupwards through the annular space of the well casing 12 as a crudehydrogen stream. In other words, the driving force for displacing thestored hydrogen 4 is provided by the pressurized brine 315 enteringdownwards into the cavern 3 through the brine string 10. Well head valve227 is set in an open position to enable the crude hydrogen stream toenter the hydrogen storage and processing facility 1 shown in FIG. 1.The crude hydrogen is discharged as a crude hydrogen stream 21. Thecrude hydrogen stream 21 readily flows through the second leg “B” offlow network 5 and is exported into the product pipeline 2 with valve 23set in the open position. In still another variation, not all of thestored hydrogen 4 need be removed. Brine 315 can be injected into thecavern 3 as described above so as to establish a specific cavernpressure in between the lower pressure threshold and the upper pressurethreshold to maintain the substantially impermeable permeation barrier.The addition of brine 315 occupies the bottom portion 207 of cavern 3(FIG. 3) and reduces the effective volume of the stored hydrogen 4contained therein. The reduction in volume compresses the storedhydrogen 4, thereby increasing the cavern pressure to the desiredpressure level that is within the lower and upper limits. In thismanner, substantially impermeable permeation barrier 206 can beeffectively formed and maintained.

When a sufficient amount of product hydrogen from the product pipeline 2is to be stored in hydrogen cavern 3, as may occur, for example, as aresult of hydrogen production exceeding customer demand, the brine 315within the salt cavern 3 can be returned to the brine pond 301. In apreferred embodiment, product hydrogen is drawn off from the pipeline 2,compressed and injected into the cavern 3. Compression by compressor 7ensures that the product hydrogen stream has sufficient driving force todisplace the brine 315 from out of the cavern 3 into return leg “D” offlow network 318 (FIG. 3). Valve 24 (FIG. 1) is open to allow a portionof the product hydrogen in pipeline 2 to enter leg “A” of flow network 5as hydrogen product stream 13. Valve 20 is closed, and bypass valve 14is set in a closed position to allow the hydrogen product stream 13 tobe compressed by compressor 7 to form a compressed hydrogen productstream 16. Valve 15 is open to allow the compressed hydrogen productstream to flow through well casing 12 and thereafter enter cavern 3.

The compressed hydrogen stream 16 is introduced into the salt cavern 3to form the stored hydrogen 4. The compressed hydrogen stream 16continues to flow through the first leg “A”. The compressed hydrogenstream 16 thereafter enters conduit 12 (FIG. 2), which is connected to atransfer well head assembly 202, and thereafter into an annular flowarea (not shown) within final well casing 12 (between the inside offinal well casing 12 and brine string 10) from which the compressedhydrogen feed stream 16 enters salt cavern 3. As the compressed hydrogenproduct enters salt cavern 3, the brine 315 stored therein is displacedupwards through the well casing 12. Valve 303 is opened, and valve 304is closed to allow the brine 315 to flow as stream 317 through thereturn leg “D” of flow network 318 of the brine pond system 300 into thebrine pond 301. A pump may be employed to pressurize brine stream 317,if necessary. In this manner, the return of the brine 315 to the brinepond 301 is possible.

As an alternative to the above described brine pond system 300, itshould be understood that the present invention also contemplatespermanently retaining a minimal amount of brine 315 along the bottomportion 207 of the cavern 3 so that brine 315 does not need to betransported to and from a brine pond 301. The preferred amount of brine315 to be permanently retained at the bottom portion 207 of the cavern 3would be that amount which is equivalent to reduce the effectivehydrogen storage volume of the cavern 3 such that the compression of thecavern volume is always pressurized slightly above the lower limitpressure threshold. In such an embodiment of the present invention, onlythe upper limit for the cavern pressure threshold would need to beregulated to ensure formation of the substantially impermeablepermeation barrier 206 without fracture of the salt walls 203. Cavernpressure and temperature can be monitored with suitable instrumentationas has been described to ensure that the substantially impermeablepermeation barrier 206 at the lower limit is being maintained by thebrine 315 and at the upper limit by introduction of hydrogen from thepipeline 2.

Other techniques for forming and maintaining the substantiallyimpermeable permeation barrier 206 of the salt cavern 3 arecontemplated. For example, a controlled amount of heat can be impartedto the salt walls 203 to cause the walls 203 to attain a state ofplasticity in which a portion of the walls 203 begin to move, thusclosing and sealing any pores, voids and/or microfractures within thesalt walls 203. The amount of heat that gets transferred from thecompressed hydrogen stream 16 to the walls 203 can vary, depending uponthe crystal and grain structure of the salt walls 203, the compositionof the salt itself and other operating factors, such as the quantity ofresidual brine remaining in the cavern 3 and from the throttling of theaftercooler 10. Preferably, the amount of heat needed to sufficientlyproduce a rise in the temperature in the cavern 3 at a particular depthof cavern 3 should be greater than the natural geothermal temperaturegradient of the earth that corresponds to the particular depth of cavern3. The amount of temperature rise needed to create this sealingmechanism and drive the salt to a more plastic physical state may beabout 0.1° F./linear foot of depth of the cavern 3, denoted as “d” ofFIG. 2, or 250° F. for the cavern being referenced in this embodiment.The portions of the walls 203 can become fluid-like when heated by thehydrogen stream 16 to fill in at least a portion of the porous walls203, thereby creating a more densified wall 203 that is less permeableto the flow of stored hydrogen 4 therethrough. The temperature ofcompressed hydrogen stream 16 can be modulated by controlling the rateof cooling from the aftercoolers 10 situated downstream of thecompressor 7. In one example, the temperature of the compressed hydrogenstream 16 can be controlled to be greater than 200° F., but less thanabout 400° F., by momentarily shutting off the aftercoolers 10 for apredetermined time. As the hotter hydrogen stream 16 is introduced intothe cavern 3, it contacts the cooler walls 203, thereby heating thecooler walls 203. A portion of the walls 203 is heated and can becomesufficiently plastic-like to enable filling in of some of the porousmaterial, thereby altering the microstructure of the salt walls 203. Inparticular, the temperature of the salt walls 203 increases as heatdiffuses therein. The heating causes grains to combine with each other.As a result, the grain sizes are increased, and the number of grainboundaries decrease. The reduction in grain boundaries creates fewerdiffusion pathways for the stored hydrogen 4. A less porous structure isthereby created in which the number of pores and size of the pores ofthe walls 203 can both be decreased. This transfer of heat from thecompressed hot hydrogen stream 16 to the salt walls 203 can potentiallyreduce the impact of stress dilation and micro fracturing of the salt203, thereby strengthening and improving the properties of thesubstantially impermeable permeation barrier 206. Such a temperaturetreatment to the cavern 3 can be conducted one or more times as neededto suitably alter the grain microstructure of the salt walls 203.

In an alternative embodiment, a method for enhancing confinement of thestored hydrogen within the substantially impermeable permeation barrier206 of the salt cavern 3 can be achieved by ensuring an adequate sealbetween the casing 12 and cavern 3 is maintained during the service lifeof the salt cavern 3. The casing 12 is generally made of steel or steelalloy such as carbon steel. The casing 12 is typically cemented intoposition and forms a seal with the top portion of 204 of the cavern 3.However, exposure to hydrogen can cause the steel or steel alloyedcasing 12 to undergo hydrogen embrittlement. Mechanical stress in casing12 due to hydrogen embrittlement can reduce the ductility of the casing12, which can lead to brittle failure of the casing 12, thus creatingresidual stresses. The residual stresses within the casing 12 can behigh enough to push against the top portion 204 and potentially creategaps that destroy the seal between casing 12 and the top portion 204 ofthe cavern 3. The gaps create a flow path for the stored hydrogen 4 toexit therethrough. As such, the structural integrity of the cavern 3 iscompromised and the cavern 3 can become inoperable.

To counteract hydrogen embrittlement, hydrogen product that is removedfrom the pipeline 2 for storage in the cavern 3 can be compressed bycompressor 7 to produce compressed hydrogen stream 16. However, ratherthan remove the heat of compression, all of the heat of compression or asubstantial portion of the heat of compression is maintained within thecompressed hydrogen stream 16 by regulating the after cooling rate ofthe compressed stream 16 through various heat exchange equipment (i.e.,after coolers, fin fans, or other suitable means as known in the art).For example, an after cooler 10 situated downstream of the compressor 7as shown in FIG. 1 can be throttled to manipulate the temperature of thecompressed hydrogen stream 16 so that all of the heat of compression ora substantial portion of the heat of compression is maintained withinstream 16.

As the compressed hydrogen stream 16 flows through the well casing 12, asufficient amount of heat is transferred to the steel or steel alloyedcasing 12 and increases the temperature of the well casing 12 asufficient amount to both increase the ductility of the casing 12 andsuppress the onset of hydrogen embrittlement along the casing. It shouldbe understood that the term “suppress” as used herein means a reductionor delay of hydrogen embrittlement. The heated temperature of the wellcasing 12 can vary depending on the particular steel alloys utilized. Ina preferred embodiment, the well casing is carbon steel which is heatedto a temperature from about 200° F. to about 400° F.

In this manner, the seal between the casing 12 and the cavern 3 remainsstructurally in-tact during the service life of the cavern 3 to improveconfinement of the stored hydrogen 4 by the elimination or substantialreduction of hydrogen leakage through gaps between the casing 12 and thetop portion 204 of the cavern 3.

It should be understood that various modifications to the presentinvention are contemplated without departing from the spirit and scopeof the present invention. For example, a portion of the hydrogen productthat is removed from a pipeline 2 may be sufficiently pressurized,thereby eliminating a need for its compression. Particularly, a portionof the hydrogen product that is removed from the hydrogen pipeline 2 canbypass the compressor 7, and thereafter be introduced into the saltcavern 3. As the pressure in the cavern 3 increases and begins todeviate from predetermined compression requirements (e.g., pressure inthe cavern 3 approaches or exceeds the pressure in the hydrogen pipeline2), additional hydrogen product which is removed from the hydrogenpipeline 2 may require pressurization and can therefore be compressed bythe compressor 7 prior to its introduction into the salt cavern 3.Additionally, it should be understood that stored hydrogen 4 can bewithdrawn from the cavern 3 and re-routed to the compressor 7, ifrequired to pressurize the withdrawn hydrogen to a sufficient pressureequal to or greater than the pressure of the pipeline 2. In this manner,the compressor 7 can be selectively utilized to introduce hydrogenproduct into the cavern 3 and withdraw stored hydrogen 4 from the cavern3, as necessary during operation of the cavern 3. Additionally, theintroduction and withdrawal of brine or other gases into the cavern 3for preferably reducing the effective volume of the cavern 3 may alsooccur in a similar manner.

While the present invention has been described in relation to theability to store hydrogen at purity grades of preferably about 95% andhigher, it should be understood that the principles of the presentinvention also are applicable to storage of lower purity grades ofhydrogen (i.e., below 95% purity) as well as other non-hydrogencontaining gases, including inert gases, and any combination thereof. Inaddition to confinement, the present invention can substantially reducepermeation of contaminants from the walls of the salt cavern 3 into thestored gas, thereby mitigating concerns of contamination typicallyencountered when maintaining stored gas within conventional saltcaverns. The ability to reduce contamination of the stored gas may insome instances eliminate the need for implementation of purificationequipment upon withdrawal of the stored gas from the salt cavern 3. As aresult, the present invention offers a process benefit of substantialreduction in cost and complexity of operating the salt cavern 3. Stillfurther, hydrogen product may be removed from various hydrogen sources.By way of example, hydrogen product may be removed from a hydrogenproduction source, such as one or more stream methane reformers, andthereafter introduced by a hydrogen pipeline into the salt cavern 3. Inanother example, the hydrogen product may be removed from a hydrogenrecovery plant and directed by a hydrogen pipeline into the salt cavern3. Alternatively, hydrogen product may be removed from any type ofhydrogen storage source and routed by a hydrogen pipeline into the saltcavern 3.

EXAMPLE

A mechanical integrity test was conducted to evaluate and verify thestructural integrity of a salt cavern for storing hydrogen in accordancewith the principles of the present invention. FIG. 5b shows thetest-setup. A gaseous hydrogen stream was withdrawn from hydrogenpipeline, compressed and then injected into the cavern 3 as a compressedstored hydrogen 504, in a similar manner as described in FIG. 1. Apressure transducer (e.g., as shown in FIG. 2) was used to monitor andregulate the pressure of the stored hydrogen 504 to ensure that thepressure was maintained above the minimum limit but below the upperlimit. As a result, a substantially impermeable permeation barrier 506was formed and maintained throughout the mechanical integrity test. FIG.5 shows that the substantially impermeable permeation barrier 506extended continuously along the walls of the cavern 500.

Downhole retractable temperature gauges and instrumentation wereinserted into the cavern 3 at various depths to generate a temperatureprofile gradient as a function of cavern depth, “d” (shown in FIG. 5a ).The temperature gauges were also utilized to detect leakage of hydrogenon the basis of any temperature excursions in the cavern 500. Thetemperature excursions occur because hydrogen has a negativeJoule-Thompson coefficient upon volume expansion. FIG. 5 shows one ofthe temperature gauges 501 that were inserted through well casing 502within the interior volume of salt cavern 500. The temperature gauge 501and the other gauges (not shown, for purposes of clarity) werecalibrated to accurately and precisely detect temperature excursions onthe order of 0.01° F. or more. Placement of the temperature gauges atdifferent depths within the cavern 3 allowed for the capability todetect localized leaks, including those from the well casing 502. Theoutput signal 507 from the temperature gauge 501 and others (not shown)were coupled to an active control system 508 configured to close thecavern's emergency shutdown valves located within cavern wellheadassembly 202 (FIG. 2), if necessary, as a result of leakage detection.Accompanying high temperature alarms were programmed into the controlsystem 507. Similarly, alarms for low and high pressure limits wereprogrammed into control system 508. The temperature gauges utilized inthe test provided accuracy within plus/minus 0.1° F., and the pressuregauge utilized in the test provided accuracy to within plus/minus 0.05%.

The pressure and temperature readings were compiled for 72 continuoushours. The downhole pressure and temperature readings obtained at adepth of 50% of the cavern depth, d, were employed to calculate thevolume of stored hydrogen 504 within the salt cavern 500 at the start ofthe test and at the conclusion of the test. Any measurement error, asindicated by the inherent accuracy and precision of the temperaturepressure gauges and instrumentation, were factored into the gas volumecomputation. The results indicated that the volume of stored hydrogen504 at the start of the test was equal to the total volume of storedhydrogen 504 at the end of the test. Further, the temperature profilegradient shown in FIG. 5 was linear and did not exhibit any discernibletemperature excursions. The results supported the conclusion that thesubstantially impermeable permeation barrier 506 was formed andmaintained during the 72 hours test window.

The ability of the present invention to store ultrahigh purity hydrogenwithout volume losses of the stored product is an improvement overconventional storage methods. Furthermore, the substantially impermeablepermeation barrier reduces seepage and leakage of the hydrocarboncontaminants from the salt walls 203 into the stored hydrogen volume,potentially reducing the costs associated with implementing suitablepurification equipment for the subsequent withdrawal of the storedhydrogen 4. For example, the required sizing of adsorption beds in thepresent invention would be potentially smaller than of conventionalstorage caverns, as less contaminants would be required to be removedupon withdrawal of the stored hydrogen 4 from salt cavern 3 to achieve aproduct purity specification. In conventional storage caverns, theinherent porosity of the salt walls 203 may contribute to introductionof a large amount of contaminants from the salt walls 203 into theinterior of the cavern 3, thereby requiring larger purification units(e.g., adsorption units). Accordingly, the present invention offers aunique process benefit with respect to the amount of purificationrequired when the stored hydrogen gas 4 is withdrawn from the cavern 3.Such a process benefit translates into a more cost effective hydrogenstorage processing facility relative to conventional salt cavernhydrogen storage facilities.

While it has been shown and described what is considered to be certainembodiments of the invention, it will, of course, be understood thatvarious modifications and changes in form or detail can readily be madewithout departing from the spirit and scope of the invention. It is,therefore, intended that this invention not be limited to the exact formand detail herein shown and described, nor to anything less than thewhole of the invention herein disclosed and hereinafter claimed.

The invention claimed is:
 1. A method for storing high purity hydrogenproduct in a salt cavern, the salt cavern containing walls characterizedby a halite structure having a minimum purity of at least about 75% ofsodium chloride, comprising: removing the high purity hydrogen productfrom a high purity hydrogen pipeline; compressing the high purityhydrogen product to produce a compressed high purity hydrogen productcomprising a purity of 99% or greater; introducing the compressed highpurity hydrogen product into the salt cavern to create a pressurebetween a predetermined lower limit and a predetermined upper limitwithin the salt cavern; maintaining the pressure within the salt cavernbetween the predetermined lower limit and the predetermined upper limit,wherein fluid is introduced into the salt cavern to increase thepressure within the salt cavern to at least the predetermined lowerlimit but below the predetermined upper limit, wherein the predeterminedlower limit is 0.2 psi per linear foot of cavern depth and thepredetermined upper limit is 1.0 psi per linear foot of cavern depth,wherein the cavern depth is defined as the vertical distance spanningfrom a top-most portion to a bottom-most portion of the salt cavern; andconfining the high purity hydrogen product within the salt cavern. 2.The method of claim 1, wherein the predetermined lower limit is 0.4 psiper linear foot of cavern depth and the predetermined upper limit is0.85 psi per linear foot of cavern depth.
 3. The method of claim 1,wherein the step of maintaining the pressure includes withdrawing aportion of the high purity hydrogen product from the salt cavern.
 4. Themethod of claim 1, exhibiting temperature excursions of less than 4° F.for pressure losses of less than 1200 psig in the salt cavern.
 5. Themethod of claim 4, exhibiting no discernable temperature excursions. 6.The method of claim 1, further comprising the steps of: compilingpressure and temperature readings within the salt cavern for a testperiod of 72 hours; calculating the volume of high purity hydrogenproduct stored in the salt cavern and the volume of high purity hydrogenproduct within the salt cavern at the start of the test period to beequal to the volume of high purity hydrogen product in the salt cavernat the end of the test period.
 7. The method of claim 6, exhibiting nodiscernable temperature excursions.
 8. The method of claim 1, whereinthe fluid comprises brine.